Photographic silver halide emulsion

ABSTRACT

wherein D represents a divalent aromatic group combining with each other the pyromidinylamino groups or triazinylamino groups shown in the above formula, R3, R4, R5 and R6 each represents a hydrogen atom, a hydroxyl group, an alkoxyl group, a halogen atom, an amino group, an alkyl amino group or a substituted alkylamino group, such as, a hydroxyalkylamino group, a sulfoalkylamino group, a cycloalkylamino group, an arylamino group and a heterocyclic amino residual group, and W represents CH- or N-.   wherein Z1 represents the nonmetallic atoms necessary for forming 4-quinoline nucleus, Z2 represents the nonmetallic atoms necessary for forming a 5or 6-membered ring, R1 and R2 represent substituted or nonsubstituted alkyl groups, X is an acid anion group, M IS 1 OR 2, AND P IS 1 OR 2, SAID DYE FORMING AN INTRAMOLECULAR SALT WHEN P IS 1, AND TOGETHER WITH A COMPOUND HAVING TRIAZINE NUCLEI OR PYRIMIDINE NUCLEI REPRESENTED BY THE FOLLOWING GENERAL FORMULA II:   A photographic silver halide emulsion having incorporated therein the sensitizing dye represented by the following general formula I:

United States Patent Keisuke Shiba;

Masanao llinata; Reiichi Ohi; Hiroshi Misu, all of Kanagawa, Japan [21] AppLNo. 680,024

[22] Filed Nov. 2,1967

[45] Patented 0ct.26, 1971 [73] Assignee FujiPhoto-Film Co., Ltd.

[72] Inventors Kanagawa, Japan [32] Priority Nov. 2,1966 [3 3 1 Japan [54] PHOTOGRAPHIC SILVER HALIDE EMULSION 9 Claims, No Drawings [52] US. Cl 96/130, 96/122 [51] Int. Cl G03c 1/10 [50] Field of Search 96/ 102,

(56] References Cited UNITED STATES PATENTS 2,945,762 7/1960 Carroll et al 96/100 OTHER REFERENCES Cyanine Dyes and Related Compounds, Ham'er, page 88, QD40l H25 Primary ExaminerWilliam D. Martin AssistantExaminer-Theodore G. Davis Attorney-Sughrue, Rothwell, Mion, Zinn & MacPeak ABSTRACT: A photographic silver halide emulsion having incorporated therein the sensitizing dye represented by the following general Formula 1:

wherein D represents a divalent aromatic group combining with each other the pyromidinylamino groups or triazinylamino groups shown in the above formula,

R R R and R, each represents a hydrogen atom, a

' hydroxyl group, an alkoxyl group, a halogen atom, an amino group, an alkyl amino group or a substituted alkylamino group, such as, a hydroxyalkylamino group, a sulfoalkylamino group, a cycloalkylamino group, an arylamino group and a heterocyclic amino residual group, and

W represents CH- or N-.

PHOTOGRAPI-IIC SILVER HALIDE EMULSION BACKGROUND OF THE INVENTION l. Field of the Invention The present invention relates generally to a spectrally sensitized photographic silver halide emulsion and more part icularly to a spectrally sensitized photographic silver halide emulsion in which the formation of photographic fog has been suppressed and the reduction of the spectral sensitivity during long storage has been prevented.

2. Description of the Prior Art I! is well known in the producton process of photographic silver halide emulsions that by incorporating a certain kind of sensitizing dye in a silver halide emulsion, the light-sensitive wavelength of the silver halide emulsion is extended to a longer wavelength region. This is technically called spectral sensitization. The intensity of the spectral sensitization is influenced not only by the chemical stnlcture of the sensitizing dye, thepropertiesofthe emulsion, such as, the composition of the silver halide, the crystal structure of the silver halide, the concentration of silver ions in the emulsion, the pH of the emulsion and the like, but also by the kinds of stabilizers, wetting agents, hardening agents, and couplers present together in the emulsion. In most cases, these compounds incorporated in the silver halide emulsion other than the sensitizing dye are apt to reduce the spectral sensitization. Also, while a sensitizing dye is able to sensitize spectrally the emulsion when added to the emulsion, the addition thereof to the silver halide emulsion is usually accompanied with certain faults such as the formation of fog, the reduction of the property of keeping spectral sensitivity and the like. Therefore, in order to prepare a photographic silver halide lightsensitive element showing less fog and having a good keeping property, it is highly necessary to inhibit the formation of fog caused by the addition of a sensitizing dye and improve the reduction of the spectral sensitivity, which occurs during the long storage. However, the use of a conventional antifoggant or a stabilizer for improving drawbacks of the emulsion itself, usually results not only in a remarkable reduction in spectral sensitivity, but also in a decrease in the property of keeping spectral sensitization. Therefore, it must be emphasized that the combination of a sensitizing dye with various kinds of additives to improve the property of the emulsion itself should be selective in order to improve the above-mentioned faults in the spectrally sensitized materials.

Therefore, an object of the present inventionis to provide a photographic silver halide emulsion which has been spectrally sensitized and in which the formation of fogging by dyes and also the deterioration in the spectrally sensitizing property of the dye, in the course of storage, have been prevented without reducing substantially the spectral sensitivity itself.

SUMMARY OF THE INVENTION The object of this invention can be accomplished according to the present invention by incorporating in a photographic silver halide emulsion the sensitizing dye represented by the following general formula I:

X is an acid anion group,

m is l or 2, and

p is l or 2, said dye forming an intramolecular salt when p is l, and together with a compound having triazine nuclei or pyrimidine nuclei represented by the following general wherein D represents a divalent aromatic group combining with each other the pyromidinylamino groups or triazinylamino groups shown in the above formula.

R,, R, R and R each represents a hydrogen atom, 5 hydroxyl group, an alkoxyl group, a halogen atom, an amino group, an alkyl amino group, a substituted alkylamino group, such as, a hydroxyalkylamino group, a sulfoalkylamino group, a cycloalkylamino group, an arylamino group and a heterocyclic amino residual group, and

W represents CH or =N- In aforesaid general formula I, Z, may be 4-quinolinc nuclei having a substituent, such as, a halogen atom, an alkyl group, an alkoxyl group and the like. Z is a nonmetallic atomic group necessary for forming a heterocyclic nucleus, such as, a 4- quinoline nucleus, a Z-quinoline nucleus, a naphthothiazole nucleus, a napthoselenazole nucleus, a naphthoxazole nucleus, a benzoselenazole nucleus, a benzothiazole nucleus, a benzoxazole nucleus, a thiazole nucleus, an oxazole nucleus, and the like. R, and R may be a lower alkyl group, such as, a methyl group, an ethyl group and a propyl group; substituted alkyl group, such as, B-hydroxyethyl group, a B-acctoxyethyl group, an ethylsulfate group; and the like; a carboxylalkyl group or a derivative thereof such as, a carboxyethyl group, a 2-(2-carboxyethoxy)ethyl group and the like; or a sulfoalkyl group and a derivative thereof, such as, a B-sulfoethyl group, a -y-sulfopropyl group, a 2-hydroxy-l-sulfopropyl group, a 3- methoxy-2-(3-sulfopropoxy)propyl group and the like. One structural feature of the sensitizing dye in this invention is that the dye includes at least one quinoline hetero nucleus.

In formula II, D may be any divalent atomic group which combines the pyrimidinylamino nuclei each other or the triazinylamino nuclei each other in the above-mentioned formula I], such as, a biphenylene group, a phenylene group, a naphthylene group, a stilbene group, a bibenzyl I group and the derivatives thereof.

The feature of the compound shown in general formula II is in a point that the compound has the pyrimidinylamino nuclei or the triazinylamino nuclei bridged to each other by the aforesaid atomic group D.

The sensitizing dye represented by general formula I can sensitize spectrally in a region from a green to red arbitrarily by selecting two heterocyclic nuclei. In particular, the sensitizing dye used in this invention can spectrally sensitize a silver halide emulsion stronger than the case of using a dye having no quinoline nucleus. Even though the sensitizing dye is a trirnethine cyanine dye, it can strongly sensitize spectrally a silver halide emulsion even up to the red region which can be attained by using a pentamethine cyanine dye. Also, many of the sensitizing dyes used in the present invention show M- band type spectral sensitization and such spectral distribution is quite suitable to use in a red-sensitive emulsion layer. On the other hand there are faults, such as, fog caused by the dye is easily formed and the spectral sensitivity obtained tends to be lowered in the course of storage. However, when the sensitizing dye shown by general formula I is incorporated in a silver halide emulsion layer along with the compound shown by general formula II having substantially no absorption in a visible region and having a strong absorption in a near ultraviolet region, the formation of fog by the dye can effectively be inhibited and the reduction in spectral sensitivity in the course 3 4 of storage can be almost completely prevented without sub- (ID) stantially reducing the spectral sensitivity itself. That is, the S compound shown by general formula II not only prevents the reduction of the spectrally sensitizing property of such a J trimethincyanine dye showing M-band type spectral sensitiza- 5 l tion but also markedly increase the spectral sensitivity. This means that the compound shown by general formula II shows surely a remarkable super-sensitizing action in this invention. In general. it is known that super-sensitization is apt to occur in the case of .l-band type or H-band type trimethine cyanine dye, while it is unfamiliar that the compound shown by general (Ila) mum l on Hr formula ll shows such a remarkable super-sensitization with SIOJNE the sensitizing dye of this invention having M-band type spec- N tral distribution, which is one of the important features of this NH w invention. Further, by using the sensitizing dye shown by N l Id h general formula I, along with the compound shown by general formula ll, the color stain formed by the sensitizing dye after photographic processing is reduced and also the harmful action of co pler present therewith on the spectral sensitization N -l( W is less. These also are features of the invention.

The compound shown by general formula I and the com J k/ pound shown by general formula II may be incorporated into a silver halide emulsion separately or together as a solution in a water-soluble organic solvent such as, methanol, ethanol, or alkaline methanol, or as an aqueous solution. In general, the

amounts of the compounds shown by general formula I and (11b) general formula II to be added to a silver halide emulsion may N be controlled according to the properties of these compounds, NHU NH CHTCH' the properties of the emulsion, the kinds of additives to be N I \I added to the silver halide emulsion together with the dyes and a the like. They may be used in various ratios.

The silver halide used in the silver halide emulsion may be silver iodobromide, silver chlorobromide, silver chloride and the like. Also, the silver halide emulsion of this invention may he prepared in a conventional manner and may be applied to a g g l N I proper support, such as, a film of a cellulose derivative, a

baryta paper and the like.

In the case of incorporating the compounds shown by the Nllml/ aforesaid general formula I and ll in combination to a silver 40 R) halide emulsion, it is particularly effective to apply to a redaN sensitive emulsion for color photographic light-sensitive 5 materials. N

Typical examples of the sensitizing dyes shown by general formula I and ll are shown below, but it should be understood Q that the sensitizing dye used in this invention is not limited to them only.

IA Q Q l 0 mcz-N =CHCH=CH table I.

Among the compounds shown by general formula ll and TABLE 1 used in thi: 1vention, the compound wherein W in said forsensitizing supersensi mula is N that is, the compound having an s-triazine may y fi r, ml. 1 be prepared by a known method. The compound wherein W is Test I 5T Iii; if; CH=, the compound having the pyrimidine nuclei may be 5 prepared by a similar method to the case of preparing com- 1 pound He and compound llb as shown below. %2 l 2 IB 100 n 0.04 PREPARATION OF COMPOUND He 10 IB 1 87 100 u. h: IB 3 103 115 0. hl To I00 ml. of acetone and 100 ml. of water were added g g f-f l 12.4 g. of sodium 4,4'-diaminostilbene-2,2-disulfonate and IB 3 100 170 0.57 l 1.0 g. of 2,4,6-trichloropyrimidine and the mixture was 3 H 1B 3 11b )0 Us I W stirred at 5565 C. While neutralizing hydrochloric acid IB 3 I11) 4 100 106 0.01) formed with the advance of the reaction by adding dropwise 4 1B 3 He 2 100 U a an aqueous solution of percent sodium carbonate, the reac- IB 3 He 4 100 u: 45 tion mixture was maintained at a state of from neutral to weak 5 1B 3 d m0 153 L acid. After the end of reaction, the reaction produced was 13 3 I 1 10 115 l 35 cooled by ice to precipitate a crystal, which was recovered by 6 H 3 m H5 35 filtration to provide the product. 173 3 I l ii 1 7 IC 0 1h 11m 0 um 10 1 Ho 71 muv 0.01 PREPARATION OF COMPOUND llb V 1 l I. .A solution of l7.8 g. of compound lle and 5.7 g. of [3- fi naphthylamine in I00 ml. of dimethyl formamide was 1 for 3-4 hours under refluxing. After cooling, the product was 8 18% 8 desalted by filtration in nitrogen and then neutralized with an ID 3 Ilb 100 240 n: in; aqueous solution of IO percent sodium carbonate. Thereafter, h; lg? the unrcacted amine was removed by extracting with benzene ID 3 11d 0a 500 11:01 and the solvent of dimethylformamide and water was removed 9 IE 0 nd H 100 0 u m from the system by distillation under a reduced pressure. IE 1 11d 100 100 0. 05 Then, 20 g. of the residue prepared above was heated for 3 g hours under refluxing in 100 ml. of aniline and the reaction IE {1 Mb 2 79 17s 0.011 product mixture was added to about 250 ml. of methanol to IE 5 Mb 4 105 precipitate the crystal of the objective compound, which was by l f Note: (A)=Sensitizing dye; (B)=Addition amount of the The present lnventlon w|ll now be explamed by referring t sensitizing dye; (CFCompound Show by genflal Formula I; the followmg pract'cal examples (D)=Addition amount of the compound; (E)=Blue sensitivity 40 8,; (F )=Spectral sensitivity; (G )=Fog. EXAMPLE I From the results shown above, it will be clear that by applying the present invention, a photographic silver halide emul- A methanol solution of 4x10" mols of the sensitizing y sion is produced in which the formation of fog is inhibited shown by general formula I was added to 100 g. of a silver ith tl i g the spectra] Sensitivity. iodobromide emulsion prepared by a conventional method, which contains Ag X by 33x10" mols, and furthermore, a EXAMPLEZ methanol solution of l l0' mols of the compound shown by To 100 of a silver chlorobmmide emulsion re med b a general formula ll was immediately added in the amount conventioil method which contains g x y 2 i Show in i The emulsiim thus prepare! was stirred for l were added a methanol solution of 4X I O mols of the sensitizhour at 40 and applied to a SuPpon m an amount of 7 ing dye shown by general formula I and a methanol solution of of emulslon per.cabmet a and i l l0 mols of the compound shown by general formula ll in Thus prepared hght'sensmve matenal was exposed by an the amounts shown in table 2 respectively The resultant emuloptical wedge through a blue filter passing only light of a sion was stirred for 30 minutes at 40 C. and, with the addition i l Shner.than 500 and through a yellow of a hardening agent and a wetting agent, the finished em ulmer passlpg only of a wavelength lqnger than I sion was applied to a film base and dried. The light-sensitive The materlalwas then developed for 10 minutes at 20 C. m a mm thus prepared was placed under a relative humidity of black and whne developer Show" as follows: -70 percent at 2430 C., for the long duration shown in table 2 and then the spectral sensitivity S was measured by COMPOSlTlON OF THE DEVELOPER using such a yellow filter, as in example I. The results are 60 shown in the following table 2.

Methanol 0.3 3 Potassium methahinulfi e 1.4 Sodium sull'ltc (anhydrous) 38 g. TABLE 2 fly q 6 s 6 5 Shnsltlzlng Super-sensi- Sodium carbonate (mnmrhydrate) 22.5 g (lye, ml. tlzm'. 1111. (E1 i ilili l illr 'l'ufll'. N. (A) (n) (c) (m (11) (h) (M Wale: In mulw l,lll|0 ml I IA 3 H n In" TS (in M 'l llu '3 Hill h; IA l Hit 1 M as .\.i J H l Ill 0 mo 77 1;! It l III 2 22: Jun um This was followed by fixing. Further, the optical density obi taincd was measured and the blue sensitivity S, and the spec- {T f f; i n "m 3 tral sensitivity S,,,,, were measured. The results are shown in Note; (A Sensitizing dye; (B): Addition amount of the sensmzing dye; (C Compound shown by general formula I]; (D Addition amount of the compound; (E): Relative spectral sensitivity Sopt; (a) Directly after coating; (b) After I month; (c) After 4 months.

From the results shown above, it will be clear that by applying the present invention, a photographic silver halide emulsion is produced in which the deterioration of the dye sensitizing property in the course of the storage has been prevented.

What is claimed is:

l. A photographic silver halide emulsion containing at least one sensitizing dye shown by the general formula A:

wherein W represents a member selected from the group consisting of CH-and N,

R;,, R R and R each represents a member selected from the group consisting of a hydrogen atom, a hydroxyl group, a halogen atoms, an amino group, an alkyl amino group, a substituted alkylamino group, an arylamino group, and heterocyclic amino residual group, and

D represents an aromatic divalent atomic group bonding to each other the pyrimidinylamino nuclei or the traizinylamino nuclei shown in Formula B.

2. The photographic silver halide emulsion according to claim I wherein said emulsion is a red-sensitive silver halide emulsion for color photographic light-sensitive elements.

3. The photographic silver halide emulsion as claimed in claim 1 in which the 4-guinoline nucleus completed by Z, has

a substituent selected from the group consisting ofa halogen atom, an alkyl group and an alkoxyl group; and the heterocyclic nucleus completed by Z is selected from the group consisting of a 4-quinoline nucleus, a 2-quinoline nucleus, a naphthothiazole nucleus, a naphthoselenazole nucleus, a napthoxazole nucleus, a benzoselenazole nucleus, a benzothiazole nucleus, a benzoxazole nucleus, a thiazole nucleus and an oxazole nucleus; and the aromatic divalent atomic group represented by D is selected from the group consisting of 4. A photographic silver halide emulsion containing l,l diethyl-4,4'-carbocyanine iodide and at least one compound shown by the formula:

wherein W, D, R R R and R have the meanings given in claim 1.

5. A photographic silver halide emulsion containing l,l diethyl-2,4-carobcyanine iodide and at least one compound shown by the formula:

N N 12 T WNHD--NHI l-Rs W N W l R4 R0 wherein W, D, R;,, R R and R, have the meanings given in claim 1.

6. A photographic silver halide emulsion containing 3-(3- carboxypropyl)-l-ethyl-6,7-benzothia-4'-carboeyanine and at least one compound shown by the formula:

N W \l/ R4 R5 wherein W, D, R,,, R R and R have the meanings given in claim I.

7. A photographic silver halide emulsion containing 3( 3-sulfopropyl)-l '-ethyl-8'-methyl-oxa-4-carbocyanine and at least one compound shown by the formula:

RPW KFNH-D-NHW Fm l RA wherein W, D, R;,, R R and R have the meanings given in claim 1.

9. A photographic light sensitive element comprising a sup port having thereon at least one layer containing a photographic silver halide emulsion as claimed in claim I. 

2. The photographic silver halide emulsion according to claim 1 wherein said emulsion is a red-sensitive silver halide emulsion for color photographic light-sensitive elements.
 3. The photographic silver halide emulsion as claimed in claim 1 in which the 4-quinoline nucleus completed by Z1 has a substituent selected from the group consisting of a halogen atom, an alkyl group and an alkoxyl group; and the heterocyclic nucleus completed by Z2 is selected from the group consisting of a 4-quinoline nucleus, a 2-quinoline nucleus, a Naphthothiazole nucleus, a naphthoselenazole nucleus, a napthoxazole nucleus, a benzoselenazole nucleus, a benzothiazole nucleus, a benzoxazole nucleus, a thiazole nucleus and an oxazole nucleus; and the aromatic divalent atomic group represented by D is selected from the group consisting of
 4. A photographic silver halide emulsion containing 1,1''-diethyl-4,4''-carbocyanine iodide and at least one compound shown by the formula:
 5. A photographic silver halide emulsion containing 1,1''-diethyl-2,4''-carbocyanine iodide and at least one compound shown by the formula:
 6. A photographic silver halide emulsion containing 3-(3-carboxypropyl)-1''-ethyl-6,7-benzothia-4''-carbocyanine and at least one compound shown by the formula:
 7. A photographic silver halide emulsion containing 3-(3-sulfopropyl)-1''-ethyl-8''-methyl-oxa-4''-carbocyanine and at least one compound shown by the formula:
 8. A photographic silver halide emulsion containing 3-(2-hydroxyethyl)-5-chloro-1''-ethyl-thia-4''-carbocyanine bromide and at least one compound shown by the formula:
 9. A photographic light sensitive element comprising a support having thereon at least one layer containing a photographic silver halide emulsion as claimed in claim
 1. 